Reactive mono- and disazo dyestuffs suitable for dyeing modified polypropylene



United States Patent 3,502,646 REACTIVE MONO- AND DISAZO DYESTUFFSSUITABLE FOR DYEING MODIFIED POLY- PROPYLENE Luigi Canonica, Milan,Argento Crotti, Cogliate, Milan, and Giampiero Pieri, Saronno, Milan,Italy, assignors {o ftziende Colori Nazionali Afiini Acna S.p.A., Milan,ta y No Drawing. Filed July 29, 1966, Ser. No. 568,758 Claims priority,application5 Italy, Aug. 2, 1965,

Int. (:1. D06p 1/02; c091) 29/08, 31/04 US. Cl. 260186 ABSTRACT OF THEDISCLOSURE Dyestuffs having the general formula The present inventionrelates to a new class of reactive dyestuffs which are suitable for thedyeing of polypropylene modified with basic organic substances.

The invention also relates to a process of dyeing the modifiedpolypropylene (obtained by extrusion and spinning of blends ofpolypropylene with basic nitrogenated organic substances) with the abovementioned dyestuffs.

Difiiculties are known to be presented in the dyeing of polypropylenefiber which, consisting only of carbon and hydrogen atoms, is free ofany polar atoms, atom groupings or radicals, which polar radicals wouldaiford sites for chemical or physical-chemical bonds with the variousclasses of dyestuffs.

In order for a dyeing to be suitable for most commercial applications,it must exhibit, besides an adequate intensity, good uniformity, andhigh fastness to alkaline washing, to detergents, to dry cleaning and tolight.

Previous attempts have been made to modify polyolefins, particularlypolypropylene, either by dispersing in the polymer one or more metalshaving a valence at least equal to 2, generally in the form of highmolecular weight organic salts, or by copolymerization with monomerswhich render the resulting copolymer more receptive to the dyestuffs, oralternatively, by extrusion and spinning of mixtures of the polyolefinsblended with basic substances.

We have now surprisingly found a new class of dyestutfs, particularlysuitable for dyeing modified polypropylene fibers, these dyestuffs beingcapable of being firmly bonded to the nitrogen-containing basic organic3 Claimssubstance present in the polypropylene fiber produced by thelast-mentioned modification process because of the presence in thedyestuffs of the reactive radical The dyestuffs of the presentinvention, having the above reactive radical, have the general FormulaI:

wherein X and Z are each a radical selected from the group consisting of--SO CH alkyl, N0 halogen, carboxyl, hydrogen, alkoxy, dialkylamino,aryl and alkylamino; Y is either the same as Z or is the radical -N NC HR wherein R is hydrogen, SO CH an alkyl radical, an alkoxy radical, -NOor halogen: at least one of the substituents X, Y and Z representing theradical SO CH Preferred dyestuffs within the above general Formula I arethose having the Formula II:

C B (H) wherein A is -N=N or NH--, and B and C are diiferent radicalsselected from the group consisting of SO CH H and a dialkylamino group,one of B and C being SO CH radical S O a C H:

S 0 a 0 Ha (I) C H S 0 0 Ha S O a C H3 S 0:! CH3 0 @2 5 S 0 GB: Cl

The modified polyolefin fibers are prepared by extrusion of thepropylene polymer blended with organic modifiers of basic nature. Theamount (I by weight) of the basic nitrogen organic additive present inthe polypropylene fiber is between 0.05 and 15% preferably between 0.05and The basic additive consists essentially of an organic compoundcontaining one or more tertiary nitrogen atoms and optionally one ormore secondary nitrogen atoms. The additive may also contain OH groupsand may be optionally present in the fiber in a crosslinked form, e.g.in epoxy form, which improves the stability and the uniformity of thedistribution in the polyolefin filament. Theoetodecylamine+epichlorohydrin+piperazine polycondensates, and inparticular the dicyclohexylhexamethylenediamineepichloridrine-l-piperazine polycondensates, are particularly suitable.

The present invention also provides a process for the dyeing ofpolypropylene material, modified with basic erganic substances asdescribed above, with an azo dyestulf of the general formula I. By thisprocess intense dyeings characterized by high fastness particularly towet treatments, as well as to washing with soap, to dry cleaning withtrichloroethylene and perchloroethylene, and to sublimation, areobtained.

In accordance with one alternative process of the invention, the dyeingis carried out in an aqueous bath, at atmospheric pressure, at atemperature of 95-100 C. for times of between about 30 and 90 minutes.The commonly used dispersing agents may be optionally added to the dyebath. In addition, the dye bath may contain from about 0.1% to 5% (byweight of the dyeing bath) of an organic or inorganic acid substance,such as, for

example, formic acid, acetic acid, sulfuric acid, hydrochleric acid,etc.

According to an alternative process, the dyestuffs can be applied underpressure (906.7 to 2026.16 mm. Hg), at 105-130 C., preferably at ll0-l25C., for times of between about 30 and 90 minutes.

Yet another alternative dyeing process is to apply according to knowntechniques the dyestufi by foulard impregnation in the presence ofauxiliary substances (such as tiodiglycol, glycerol, etc.), followed bya development at 120 C. for a few minutes.

Optionally, auxiliary dispersing agents {such as the condensationproducts of ethyleneoxide and aliphatic alcohols) which do not deiay theexhaustion of the bath may also be used.

The dyed or printed materials are then preferably subjected to a soapingtreatment at the boiling point of the soap solution fer about 30minutes.

The following examples are presented to further illustrate the presentinvention without in any way limiting the scope thereof. Unlessotherwise indicated, all parts and percentages are by weight.

EXAMPLE 1 3.53 parts of 4-anilido-azobenzene-3'-sulfonic acid dissolvedin parts by volume of phosphorous oxychloride, were heated to 80-95 (3.,and then added, at this temperature, with stirring, within about 30minutes, to 4.17 parts of phosphoruus pentachloride. At the end of theaddition, the reaction mixture was kept under agitation for 4 hours at90-95 C. Then it was cooled to room temperature and discharged underagitation into about 400 parts by volume of icewater. After about 2hours agitation at 0 C., the mixture was filtered and washed to neutralpH with icewater. Then the filter cake, partially dried by suction onthe filter, was introduced into 20 parts by volume of methyl alcohol,cooled to 0 C., whereupon 1.7 parts by volume of 36 B. NaOH were addedthereto.

After agitation for 6 hours at 0 C. and standing for one night, themixture was filtered, washed with boiling water until the wash water wascolorless, then dried at 60 C.

4 The product obtained was a yellow powder, insoluble in Water andsoluble in organic solvents, and having the structure:

l S OaCHs It dyed polypropylene fiber modified with about 1% of basicorganic additive an intense and fast yellow shade.

EXAMPLE 2 It dyed polypropylene fibed modified with 1% of basic organicadditive in an intense and fast brown orange shade.

EXAMPLE 3 0.05 part of the dyestuff prepared in Example 1 was dissolvedin 10 parts by volume of acetone. 1 part by volume of the condensationproduct of one mol of oleic alcohol with 18 mols of ethylene oxide wasadded, and the acetone was then evaporated at 60-7 0 C.

The residue was diluted to 200 parts by volume with distilled water, and3 parts of a modified polypropylene fabric, containing 1% ofdi-cyclohexylhexamethylenediamine epichlorohydrin piperazinepolycondensate, were introduced. Then the mixture was boiled for 1 hour,followed by treatment with a 5% soap solution for onehalf hour at theboiling point.

A fabric dyed in a very intense yellow shade with very good generalfastness was obtained.

EXAMPLE 4 0.05 part of the dyestuif prepared in Example 2 was dispersedas described in Example 3. 2 parts by volume of 5% acetic acid wereadded to the dispersion and 3 parts of a modified polypropylene fabriccontaining 1% of the dicyclohexylhexamethylenediamineepichlorohydrin-l-piperazine polycondensate were introduced. Thedispersion was heated at the boiling point for 1 hour.

The soaping treatment was carried out as in Example 3.

A fabric dyed in an intense brown-orange shade having very high generalfastness was obtained.

Variations can, of course, be made without departing from the spirit andscope of the invention.

Having thus described our invention, what we desire to secure and herebyclaim by Letters Patent is:

1. A dyestuff having the formula:

wherein A is N=N or -NH, B and C are different radicals selected fromthe group consisting of -SO CH H, dialkylamino wherein the alkyl has 1to 4 carbon atoms, OCH -C H and -NO one of B andC being an SO CHradical, and D is H, --OC H or 2. The dyestuff of claim 1 which has thestructure: References Cited UNITED STATES PATENTS 2,034,668 3/1936Reindel et a1. 260-205 FOREIGN PATENTS 604,064 8/1960 Canada.

3. The dyestuff of claim 1 which has the structure: CHARLES B, PARKER,Primary Ex iner 10 D. M. PAPUGA, Assistant Examiner UNITED QTSTATESPATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,502,646 March 24,1970 Luigi Canonica et al.

It is certified that error appears in the above identified patent andthat said Letters Patent are hereby corrected as shown below:

Column 2, line 30, "C being" should read C being an lines 45 to 48, theformula should appear as shown below:

SO CH Column 3, line 40, "tiodiglycol" should read thiodiglycol Column4, line 28, "fibed""'should read fiber line 70, "-N=N" should read N=N-Signed and sealed this 5th day of January 1971.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. WILLIAM E. SCHUYLER, JR.

Attesting Officer Commissioner of Patents

